γ-nitropyrazole amide compound plays an important role in organic synthesis. It can not only be simply and highly efficiently esterified with methanol in the presence of a base, but also be simply chemically converted into biologically active compounds such as γ-amino acids, 2-pyridone and 2-pyrrolidone. Some reports referring to the asymmetrically catalyzed synthesis of γ-nitropyrazole amide are available at present.
Carlos F. Barbas III et al accomplish the asymmetric Michael addition below of pyrazole amide with a nitroalkene at −20° C. by using the thiourea derivative XIV as a chiral catalyst and chloroform as a solvent, in which the product has a yield of 34%-99%, a d.r value of 10:1→20:1 (d.r: diastereoselectivity of compounds containing two or more chiral centers), and 78%-97% ee (Angew. Chem. Int. Ed. 2012, 51, 5381).

Long Lu et al accomplish the asymmetric Michael addition below of pyrazole amide substituted with trifluoromethyl with a nitroalkane at room temperature by using the thiourea derivative 2d as a chiral catalyst and toluene as a solvent, in which the product has a yield of 71%-91%, a d.r value of 4.4:1-9.9:1 (d.r: diastereoselectivity of compounds containing two or more chiral centers), and 80%-93% ee (ACS Catal. 2013, 3, 502).

Shuji Kanemasa et al accomplish the asymmetric Michael addition of an unsaturated pyrazole amide with nitromethane at −20° C. to room temperature by using R, R-DBFOX/Ph*Ni(ClO4)2*3H2O (A) and 2,2,6,6-tetramethylpiperidine (TMP) as a combined catalyst, and a mixture of nitromethane and tetrahydrofuran (v/v=1/1) as a solvent, in which the product has a yield of 39%-97%, and 77%-97% ee (J. Am. Chem. Soc. 2002, 124, 13394).

In summary, in the catalytic reaction system of Carlos F. Barbas III, the reaction needs to be carried out at −20° C., thus consuming a lot of energy. In the catalytic reaction system of Long Lu, there is a great limitation since the substrates which extending from α,β-unsaturated amides are the substrates which all substituted with trifluoromethyl at the end position. In the catalytic reaction system of Shuji Kanemasa, a step of activation at the temperature of −78° C. is needed before the start of reaction; and among the extended substrates, 11 substrates needed to be reacted at −20° C., 3 substrates needed to be reacted at 0° C., and only 2 substrates can be reacted at room temperature; the reaction time of 11 substrates is 96 hrs, and the reaction time of 6 substrates is 168 hrs; and the yield is undesirable. After the reaction, the product needed to be washed with saturated ammonium chloride and then separated and purified by column chromatography. The reaction conditions are harsh, the operation is complex, and a large amount of nitromethane is consumed (9.1 mmol nitromethane is needed per 0.1 mmol α,β-unsaturated pyrazole amide compound). Most importantly, the outcome of the reaction is undesirable. Therefore, there is an urgent need for developing an efficient, simple, energy-saving, and environmentally friendly method.